THEORY OF FORCE CONSTANTS IN METAL CARBONYLS AND THEIR DERIVATIVES

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1964

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Ohio State University

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A simple theory of the C-O stretching force constants in compounds containing a metal carbonyl group is obtained based upon molecular orbital considerations. An index to the nature of the bonding is furnished by the ratio $PI=\frac{k^{0}_{co}-k_{co}}{k^{0}_{co}-k^{\ast}_{co}}$ where $k^{0}_{co}$ is approximated by the ground state force constant in carbon monoxide and $k^{\ast}_{co}$ by that of the excited C-O molecule in the $\sigma^{2}\pi^{4}\pi^{\ast}$ configuration. Here $k_{co}$ is the force constant observed for the metal carbonyl derivative. This index provides a first estimate of the number of electrons in the anti-bonding $\pi$ orbitals of a C-O group. The index has been calculated for representative molecules with metal carbonyl groups and the results are discussed.

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Author Institution: Department of Chemistry, Purdue University

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